Alkyl monomethyl-ringsubstituted-diacetoxy-benzoate perfume compositions

ABSTRACT

The alkyl monomethyl-ringsubstituted-diacetoxy-benzoates of this invention have different and more aggressive odor notes than the corresponding dihydroxy compounds. In addition, they do not become discolored on standing or when incorporated into perfume compositions or cosmetics, a common property of chemicals having one or more phenolic hydroxyls. They may be successfully utilized to imitate or replace the scent of expensive natural oak moss products or odor notes of such products, making them novel and useful perfume materials.

United States Patent Kulka et al.

ALKYL MONOMETHYL-RINGSUBSTITUTED- DIACETOXY-BENZOATE PERFUME COMPOSITIONS Inventors: Kurt Kulka, New York; Teodosij Zazula, Rego Park, both of NY.

Assignee: Fritzsche Dodge & Olcott Inc., New

York, NY.

Filed: Jan. 31, 1974 Appl. No.: 438,248

US. Cl. 252/522; 260/473 R Int. Cl Cllb 9/00 Field of Search 252/522; 260/473 R References Cited UNITED STATES PATENTS 6/1971 Carr et al 260/473 R [451 May 20, 1975' 3,759,870 9/1973 Economy eta]. ..260/473R Primary Examiner-Veronica OKeefe Attorney, Agent, or Firm-Frank M. Nolan 57 ABSTRACT The alkyl monomethyl-ringsubstituted-diacetoxybenzoates of this invention have different and more aggressive odor notes than the corresponding dihy- 10 Claims, No Drawings ALKYL l in which R is methyl or ethyl; when the two acetoxy MONOMETHYL-RINGSUBSTTTUTED- groups are located on the second and fourth carbon DlACETOXY-BENZOATE PERFUME atoms of the ring, the methyl group is located on the COMPOSKTIONS third carbon atom of the ring; when the two acetoxy This invention relates to alkyl monomethyl-ringsub- 5 groups are located on the third and fifth carbon atoms stituted-diacetoxy-benzoates and perfume composiof the ring, the methyl group is located on the second tions containing alkyl monomethyl-ringsubstitutedcarbon atom of the ring; when the two acetoxy groups diacetoxy-benzoates. are located on the fourth and sixth carbon atoms of the In accordance with. an aspect of this invention, one ring, the methyl group is located on the third carbon or more of the alkyl monomethyl-ringsubstitutedl atom of the ring; and when the two acetoxy groups are diacetoxy-benzoates may be used with one or more located on the second and sixth carbon atoms of the other odoriferous perfume components for the producring, the methyl group is located on the fourth or fifth tion of a perfume composition. At least 1%, desirably carbon atom of the ring. 1 to 30%, and preferably 2 to 5% by weight of one or The alkyl monomethyl-ringsubstituted-diacetoxymore of the alkyl monomethyl-ringsubstitutedl5 benzoates [(1) or (2)] of this invention may be prediacetoxybenzoates having the following formula is pared by esterification of the COOH group of the coremployed: responding monomethyl substituted dihydroxy benzoic acid to the methyl or ethyl ester, followed by acetyla- CH3 tion of the two phenolic hydroxy groups.

COOK The alkyl monomethyl-ringsubstituted-diacetoxybenzoates 1) or (2)] may also be prepared by a new P and novel method of production. This novel method H h-co-d -cH involves the utilization as the starting material of a methyl-carboalkoxy-cyclohexane-dione having the formula:

in which R throughout the disclosure is methyl or ethyl.

Desirably, the other perfume component or components comprise in their entirety at least 1% by weigh 3 of the total perfume composition.

For the production of such perfume compositions, 3O (3) COOR one or more of the alkyl monomethyl-ringsubstituted- 0 O diacetoxy-benzoates are uniformly mixed with one or more of the other perfume components. The alkyl monomethyl-ringsubstituted-diacetoxy-benzoates enin which R is methyl or ethyl. hance or modify the odors of the perfume composition. The methyl-carboalkoxy-cyclohexane-dione is first They have significant aggressive odor notes and may be brominated, desirable in the form of a solution such as utilized to imitate or replace expensive natural oak solution of glacial acetic acid. The reaction which takes moss products or odor notes found in such natural place is represented as follows:

CH CH 3 COOR COOR 220R B152 Br 0 0 HO OH 9 HO OH products. The bromine solution is added slowly to the methyl- The alkyl monomethyl-ringsubstituted-diacetoxycarboalkoxy-cyclohexane-dione and its enol with benzoates are not confined in their application and can which it is in equilibrium.

be used in a variety of different perfume compositions. The reaction is desirably conducted over a period of Their usage in perfumery is only limited by the skill and about 4 hours under agitation and cooling, since the reimagination of the creative perfumer. action is slightly exothermic. Crystals of the resulting In accordance with another aspect of this invention, A alkyl monomethyl-ringsubstituted-dihydroxy-dibromocertain of the alkyl monomethyl-ringsubstitutedbenzoate precipitate and are conveniently separated diacetoxybenzoates which are novel compounds may after the addition of water, with cooling. If further puribe utilized per se for perfumes and for other purposes, fication is desired, the alkyl monomethylsuch as flavors. These novel alkyl monomethylringsubstituted-dihydroxy-dibromo-benzoate may be ringsubstituted-diacetoxy-benzoates have the formula: washed once or a plurality of times with a suitable solvent such as water.

The alkyl monomethyl-ringsubstituted-dihydroxydibromo-benzoate is debrominated by adding the benzoate, desirably precooled to a temperature of about 0C, to a dilute alkali metal hydroxide such as sodium 65 or potassium hydroxide. Desirably, the benzoate is added slowly, for example during a period of about 1 hour, to the alkali metal hydroxide solution, which is conveniently an aqueous alkali metal hydroxide solution.

COOR

To the resulting solution obtained by the treatment with the alkali metal hydroxide is added slowly, over a period of about an hour, for example, at a temperature of about C, under agitation, Raney nickel-aluminum alloy. After completion of the addition of the alloy, the reaction mixture is allowed to rise to about C and is permitted to stand for a period of about 6 hours at 0C. The Raney nickel-aluminum alloy is removed from the reaction mixture by any convenient procedure such as filtration. The resulting filtrate solution is cooled to about 0C and neutralized by any suitable acid, for example a mineral acid, such as concentrated hydrochloric acid. The resulting reaction product is separated. The aqueous part is extract once or a plurality of times To the residue is added a quantity of benzene sufficient to effect solution. The resulting solution is washed with water, once or a plurality of times, with an aqueous alkali metal bicarbonate solution such as aqueous sodium bicarbonate solution and finally with water until neutral to litmus. The solvent is removed by distillation from a steam bath under an ejector-vacuum. The crude reaction product, methyl or ethyl methyl-diacetoxybenzoate, may be purified by conventional means such as recrystallization from a solution of suitable solvent or solvents such as a mixture of equal parts of isopropanol and hexane.

The reaction which takes place in the acetylation is with a solvent such as ether. The extract is combined as follows:

(8) CH3 CH3 COOR COOR Acetylation 0 \o l I HO OH H C- O-C-CH3 with the reaction product. The resulting solution may be washed once or several times with water. The solvent such as ethyl ether may be removed by distillation from a steam bath. If purification is desired, the resulting debrominated dihydroxy benzoate may be recrystallized from a suitable solvent such as benzene. The reactions which take place are indicated as follows:

COOR

ZNaOH HO OH M210 COOR NaO ONa COOR NaO ONa Debromination with Raney nickelaluminum alloy Nat) A more comprehensive understanding of this invention is obtained by reference to the following examples:

EXAMPLE 1 Methyl 6-Methyl-2,4-Diacetoxy-Benzoate 6-met'hyl-2,4-diacetoxymethyl To produce COOR ONa

COQR

ONa

COOR ZHC]. 2NaCl HO OH benzoate, S-methyl-6-carbomethoxy-cyclohexane-1,3-

dione is initially produced.

The 5-methyl-6-carbomethoxy-cyclohexane-l ,3- dione may be prepared by reacting 1,900 g of methyl crotonate, 2,204 g of methyl acetoacetate, 437 g of sodium and 6,440 ml of methanol in accordance with the following reaction scheme:

NaOCH3 Methyl-Crotonate Methyl-Acetoacetate MOl-Wt. 100

Mol.Wt. 116

The sodium and methanol are conveniently added in the form of sodium methylate solution, which is prepared by adding gradually the 437 g of sodium to the 6,440 ml of methanol over a period of about 2 hours. The 2,204 g of methyl acetoacetate are added under agitation over a period of minutes to the sodium methylate solution at room temperature. The reaction is exothermic and the temperature rises about 12C. The reaction mixture is allowed to remain at about room temperature for about an hour after which the 1,900 g of methyl crotonate are added under agitation H3 0 CH3 ll c-ogn 0 no over a period of about minutes. The resulting reaction mixture is warmed up gradually over a period of about one-half hour to a temperature of about 70C. The reaction mixture is then refluxed with continued agitation. After approximately 30 minutes from commencement of the refluxing, the reaction becomes vigorous and heat and agitation are discontinued for about 15 minutes. After about 3 hours of reflux under agitation, the reaction mixture becomes cloudy (crystal formation). Agitation and refluxing are continued for an additional 1 hour, and the reaction mixture is then allowed to stand for several hours, such as for overnight at room temperature. The methanol is distilled off at atmospheric pressure during a period of about 5 hours and the removal of methanol is then completed under ejector-vacuum for a period of about an hour. The reaction mass is cooled to about 23C and the formed crystals are filtered off on a Buchner funnel. The crystals obtained are dissolved in about 3,800 ml of cold water under agitation. The resulting aqueous solution is placed in an ice water bath and 2,500 ml of a 20% sulfuric acid solution (pre-cooled to 20C) are gradually added under agitation over a period of minutes,

while maintaining the temperature of the reaction mass at 2022C.

Upon the addition of the sulfuric acid, crystals are C-OCH 0 ll C-OCH3 HO OH EnOl formed. After completion of the addition, agitation is continued for approximately 15 minutes. The crystals are collected on a centrifuge and washed twice with 300 ml of cold water. The crystals are centrifuged to dryness. The white crystals of 5-methyl-6- carbomethoxy-cyclohexane-1,3-dione which are air dried have a melting point of l22.5C.

The 5methyl-6-carbomethoxy-cyclohexane-1 ,3- dione is brominated to produce methyl 6-methyl-2,4- dihydroxy-3,S-dibromo-benzoate in accordance with the following reaction scheme:

OCH3

For this purpose, 368 g (2 mols) of 5-methyl-6- carbomethoxy-cyclohexane-1,3-dione and 1,384 ml of glacial acetic acid are combined and heated under agitation to 50C. A clear solution results. The solution is cooled to 20C.

The 5methyl-6-carbomethoxycyclohexanel ,3- dione and its enol may be prepared by the process of Adolf Sonn. (b.Vol.6l pp. 926-927, 1928, and Schilling and Vorlander A. Vol. 308, p. 195, 1899).

A solution of 949 g of bromine dissolved in 1,582 g of glacial acetic acid is added under agitation and cooling over a period of 4 hours, the temperature being kept between 2025C to the above prepared solution of 368 g of 5methyl-6-carbomethoxy-cyclohexane- 1,3-dione in 1,384 ml of glacial acetic acid. The solution is permitted to stand for a period of several hours, such as overnight. Crystals precipitate. There is added with agitation and cooling over a period of 45 minutes about 1,500 ml of cold water, the temperature being maintained between 2025C. The crystals of methyl 2,4-dihydroxy-3,S-dibromo-benzoate are centrifuged, washed four times with 250 m1 of water, and dried. Analysis shows a bromine content of 45.8% compared with a theoretical of 46.8%.

The methyl 6-methyl-2,4-dihydroxy-3,S-dibromobenz oate is dehrominated with Raney nickel-aluminum alloy to obtain methyl 6-methyl-2,4-dihydroxyg of sodium acetate (catalyst). The formed azeotrope benzoate in accordance with the following reaction consisting of 27.5% xylene and 72.5% acetic acid is disscheme: tilled through a 14 inches Vigreux column. The azeo- (11) CH CH3 0 Br OCH3 Debromination (LOCH3 HO OH Ho OH To p du th debrominated p u 540 g f trope distillate is about 310 ml. The temperature of the methyl 6-methyl-2,4-dihydroxy-3,S-dibromo-benzoate l flask is 125136C and the temperature of the vapor are added over a period of 1 hour to 1 1.050 ml of a sois 117l 24C.

dium hydroxide solution (pre-cooled to 2C) pre- Unreacted acetic anhydride and xylene are removed pared by dissolving 885 g of sodium hydroxide in by distillation from a steam bath under an ejectorl1,050 ml of water. There are added over a period of vacuum. The residue is dissolved in 350 ml of benzene. 1 hour to the resulting solution, maintained at a tem- The resulting solution is washed successively with 250 perature of 2C, with agitation, 473 g of Raney nickelml of water, twice with 50 ml of sodium bicarbonate soaluminum alloy (50/50%-Harshaw). After completion lution and twice with 50 ml of water. The washed benof the addition of the Raney nickel-aluminum alloy, th zene solution is neutral to litmus. The solvent is rereaction mixture is allowed to rise to 5C and is mainmoved y distillation from a Steam bath under an l tained at that temperature by cooling since the reaction tor-Vacuum- Tlie residue 0f the crude reaction Product is slightly exothermic. The reaction mixture is agitated is reerystelliled from a Solution of 170 ml of p p at 4 5C f a i d f about 6 hours It i h no] and 170 ml of hexane. The recrystallized methyl 6- mitted to stand at 0C for a period of several hours such methyl-2,4'diaeefoxyjbenzeaie has a melting P i of as overnight. The nickel catalyst is removed from the 0 56L580C- The y l is about 80% 0f the theoreticalreaction mixture by filtration on aBuchner funnel. The any of the of methyl 6'methylzi4' filtrate is refiltered to remove traces of the catalyst. dlaceioxy'hehzhate 'h thesame procedurehs The filtrate is then cooled to 0C and neutralized by the descnbed m exhmple practiced except that addition of concentrated hydrochloric acid to liberate stead of employmg 2 l of the methyl 6 methyl 2,4 dihydmxy benzoate At the carbomethoxy-cyclohexane-1,3-d1one, 2 mols of the end of the neutralization, the temperature rises to appmpnate methylcal-bomethoxy'cyclohexanedlone 15C. The aqueous solution is extracted twice with 500 ls Substituted therefor ml of ethyl ether. The ether extract is combined with a the main reaction product and the resulting solution is EXAMPLE H washed 4 times with 300 ml of water. The ethyl ether 40 Methyl y iacetoxy-Benzoate is removed by distillation from a steam bath. The re- In this method f the preparation f the methyl 3- sulting crystals'are recrystallized from benzene. The methyhzAdiacetoxwbehzoate, the 1 1 2 crystals are washed with hexane h dried- The dried dihydroxy-benzene is utilized as the starting material. crystals, methyl 6'meiliyl'2,4'd1liydT0Xy'benZ0aie, The carboxy group is first introduced into the l-.

have a melting point of 140l43C. GLC gives one th 1.2,6 -dihyd -be ene to produce 3-methylpeak. I 2,4-dihydroxy-benzoic acid. The 3-methyl-2,4-

The t y y -2, y vo aeetdihydroxy-benzoic acid is esterified to produce the ylated in accordance with the following reaction: methyl or ethyl ester of that benzoic acid. The 2 hy- CH CH l C-OCH c-ocH Acetylation; I HO OH CH -C0 0-C-CH M01 .Wt 266 TO 1365 g H101) of methyl y ydroxy groups of the ester are acetylated to produce the droxy-benzoate in a distillation flask are mixed 306 g thyl 3-methyl-2,4-diacetoxy-benzoate. (3 mols) of acetic anhydride, 563 m1 of xylene and 7.5 To produce the 3-methyl2,4-dihydroxyibenzoic acid, 124 g U101) f 2-methyl-resorcinol. 693 g washed successively with 100 ml of 5% sodium bicarmols) of sodium bicarbo a and 1,710 mi o Water are bonate solution and three times with 300 ml of water. added to a 3-necked reaction flask fitted ith thcr- The benzene in the solution is removed by distillation. mometer, agitator, reflux condenser and gas delivery Th methyl 3-methyl-2,4-dihydroxy-benzoate is crystube. The mixture is agita and heated on 8 Steam 5 tallized from 100 ml of benzene. The crystals are then bath for 2 hours at a temperature o bout The air dried. The yield is about 81.3% and the ester has a Z-rnethyl-resorcinol and sodium bicarbonate go into l i point f 125 128C,

solution. A vigorous stream of carbon dioxide is passed into the solution with the gas delivery tube reaching to The methyl 3-methyl-2,4-dihydroxy-benzoate is conthe bottom of the flask for a period of 2% hours. During 10 verted to the methyl 3-methyl-2,4-diacetoxy-benzoate the addition of the carbon dioxide, the mixture is agiby adding to a 12 liter three-necked flask fitted with tated and heated to a temperature of between thermometer, agitator and a set-up for distillation, 637 l0l-l03C. After the passage of the carbon dioxide g (3.5 mols) of methyl 3-methyl-2,4-dihydroxythrough the solution the hot reaction mixture is neubenzoate, 1,430 g(l4 mols) of acetic anhydride, 2,600 tralized immediately by adding gradually 725 ml of 15 m1 of xylene and 35 g of sodium acetate as a catalyst. concentrated hydrochloric acid for a period of about The reaction mixture is first refluxed for 2 hours under l /z hours, the concentrated hydrochloric acid being slow agitation and then the azeotrope of acetic acidadded through the gas delivery tube. The temperature xylene, boiling at 115.4C at 760 mm, consisting of at the start of the hydrochloric acid addition is about 72.5 parts of acetic acid and 27.5 parts of xylene, is rel0lC, while the temperature at the completion of the moved as it is formed by distillation over a period of 12 hydrochloric acid addition is about 70C. The reaction h Th di till ti i t i t d wh th fl k mixture is permitted to stand for several hours, such as temperature reaches 130C and the vapor temperature overnight, at room temperature. The reaction mixtur 124C. The excess acetic anhydride and xylene is then is agitated and. cooled to 10C. It is filtered on a uC removed by distillation from a steam bath in an ejector ner funnel. The resulting light-colored crystals of 3- vacuum. The crude reaction mixture is dissolved in methyl-2,4-dihydr yacid having a melting 1,000 ml of benzene and washed successively twice point of 205-206C are obtained in a yield of about with 500 ml of 5% aqueous sodium carbonate solution 64.4%. (slightly basic to litmus) and twice with 500 ml of warm The reaction hic Place 15 mdlcated as water (neutral to litmus). The solvent benzene is relows: moved by distillation from a steam bath under an ejec- Q I 0 COOH HO OH HO on CH1; 7 CH l-methyl-2 6-dihydroxy-benzene 3-methyl-2 4-dihydr oxy- (2 -met'nyl resorcinol) benzoic acid (3-methyl-beta. resorcylic acid) The crystals of 3-rnethyl-2,4-dihydroxy-benzoic acid vacuum. The reaction which are obtained on the Buchner funnel may be used a Solution f 700 1 f isopl-opanol and 700 1 f h as such without purification for the next step of esterifiaria Th Crystals are ll t d on a B h f l, cation. washed with 200 ml of cold hexane and air dried. A

To produce the methy ester Of y yield of about 71.4% of the theoretical is obtained. The dlhydl'oxy-bfinlolc 861d, 75 g of y melting point of the methyl 3-methyl-2,4-diacetoxy- 2,4-dihydroxy-benzoic acid which is obtained as debenzoate i 51 p C analysis as We as wet scribed and 800 m1 of acetone are placed in a 3-necked a aly is indicates that a pure product is obtai d reaction flask fitted with thermometer, agitator, reflux isomers of the methyl ethy1 2 y condenser and dropping funnel. The mixture is agitated benzoate ma until completely dissolved. After a clear solution is obof this example except that instead of using l-meth 1- served, 62.5 g (0.743 mol) of sodium bicarbonate are 2,6-dihydroxy-benzene as in this example the appi badded in one portion to the mixture which is then agipriate methyl-dihydroxy-benzene having the following tated and heated to reflux to the formation of a light generic formula is employed: slurry. To this mixture is added over a period of 2 hours 93.6 g (0.743 mol) of dimethyl sulfate with agitation and reflux (temperature 55--5 8C). After the addition of dimethyl sulfate is completed, reflux is continued under agitation for a period of l /2 hours. The mixture 3 is cooled to room temperature and filtered on a Buchner funnel. The acetoneis removed by distillation from a steam bath under ejector vacuum. The residue is dis- HO OH solved in 300 ml of benzene. The benzene solution is y be produced by following the procedure product is recrystallized from 3,884,843 M 12 EXAMPLE III by distillation from a steam bath in an ejector vacuum.

' The roduct is recr stallized from a mixture of 15 ml M th l4-M th l-2,6-Dh d -B t p y y e y l y roxy enzoa e hexane and 15 ml of isopropanol. The yield is 88.5% of The'immahstep of the of the methyl the theoretical. The methyl 4-methyl-2,6-diacetoxymehYLZ-6-dlhydmxy-benzoate "Wolves the producbenzoate hasamelting point of73-75C. The G. L.C.

tion' of the corresponding benzoic acid. In this initial indicates a 99 purity step, 60 g of orcinol monohydroate, 120 g of potassium bicarbonate and 120 g of glycerine are mixed together EXAMPLE 1v and agitated in a nitrogen atmosphere until solution results. Under agitation, the mixture is heated to Ethyl 3'Methyl'24'Diacetoxy'Benzoate.

115120C for 5 /2 hours in a nitrogen atmosphere. To prepare ethyl 3-methyl-2,4-diacetoxy-benzoate, The mixture is cooled. 150 ml of water are added and the ethyl ester of 3-methyl-2,4-diacetoxy-benzoic acid the mixture agitated until the solution results. The soluis first prepared. For this purpose, 301 g of 3-methyltion is then neutralized by gradual addition of concen- 2,4-dihydroxy-benzoic acid, 227 g of dry sodium bicartrated hydrochloric acid, keeping the temperature of bonate and 3,000 ml of dry acetone are mixed in a flask the reaction mixture below C. The solution is exand heated to reflux under agitation. To the agitating tracted twice with 150 ml of ethyl ether. The resulting refluxing mixture over a period of 2 hours are added ether extract is washed twice with 100 ml of water. The 416 g of diethyl sulfate. The mixture is filtered on a ethyl ether is removed by distillation from a steam bath Buchner funnel. A liquid and a solid portion result. The at atmospheric pressure. The crude reaction product is 20 solid portion is washed twice with 200 ml of benzene recrystallized from 190 ml of water. and the benzene extract is added to the liquid portion.

The reaction which takes place is as follows: The combined liquid portions are then washed twice H CH KHCO3 Glycerine HO OH HO OH 1 COOH Orcinol 4-Methyl-2 6-Dihydroxy- (Monohydrate) Benzoic Acid The 4-methyl-2,6-dihydroxy-benzoic acid has a meltwith 100 ml of warm water. The solvent is removed by ing point of 173C The yield is about 49.8% of the thedistillation and the resulting residue is recrystallized oretical. from a solution of 200 ml of benzene and 50 ml of hex- The methyl ester of 4-methyl-2,6-dihydroxy-benzoic ane. The resulting crystals of ethyl 3-methyl-2,4-dihyacid is produced by mixing together 30.2 g of 4-methyldroxy-benzoate have a melting point of 134137C. 2,4-dihydroxy-benzoic acid, 17.1 g of sodium bicarbon- The yield of about 74.4% of the theoretical.

ate and 219 ml of acetone and heating the mixture The ethyl 3-methyl-2,4-diacetoxy-benzoate is prounder agitation to reflux at a temperature of 5 75 8C. duced from the ethyl 3-methyl-2,4-dihydroxy-benzoate To the mixture are added over a period of 2 hours 25.6 by mixing together 40 g of ethyl 3-methyl-2,4-dihyg of dimethyl sulfate with continued agitation and redroxy-benzoate, 105 g of acetic anhydride, 170 g of xyflux for an additional 2 hours. The acetone in removed lene and 2 g of sodium acetate. The mixture is set up by distillation under agitation. The residue is extracted for distillation for removing the formed acetic acidtwice with ml of ethyl ether. The ethyl ether is xylene azeotrope through a 12 inch Vigreux column stripped off by distillation on a steam bath. The crude over a period of approximately 4 hours. The vapor temreaction product is recrystallized with 20 ml of benperature is 116125C. The distillate is 150 ml. After zene. The yield of methyl 4-methyl-2,6-dihydr0xy- 50 completion of the reaction,the excess acetic anhydride benzoate is about 75% of the theoretical. The methyl and xylene is removed by distillation from a steam bath 4-methyl-2,6-dihydroxy-benzoate has a melting point under an ejector vacuum. The crude reaction product of 99-100C. The V.P.C. gives one peak. is taken up in 100 ml benzene and the resulting solution The methyl 4-methyl-2,6-diacetoxy-benzoate is preis washed with 2 X 200 ml water, 50 ml of 5% aqueous pared by mixing in a set-up for distillation 18.2 g of sodium bicarbonate solution and again 50 ml of water. methyl 4-methyl-2,-dihydroxy-benzoate, 40.7 g of The solvent is removed from a steam bath under an acetic anhydride, 75 ml of xylene and 1 g of sodium acejector vacuum. The residue comprises ethyl 3-methyletate. The formed acetic acid-xylene azeotrope is re- 2,4-dihydroxy-benzoate and is recrystallized from a moved by distillation through a 6 inch Vigreux column mixture of hexane and isopropanol. The melting point at atmospheric pressure. The azeotrope consists of of the resulting crystals is 77-79C; purity by V. P. C. 27.5% xylene and 72.5% acetic acid. The time of distil- 99%, The yield is 82.3% of the theoretical.

lation requires about 2% hours. Boiling point of the Other ethyl methyl-diacetoxy-benzoates may be proazeotropic mixture is l19126C. The excess acetic duced by using the appropriate methyl-dihydroxyacid and xylene is then removed by distillation in an benzoic acid and diethyl sulfate, following the proceejector vacuurrl, The residue of the crude reaction d re in thi Exam le,

product is dissclived in ml of benzene and washed The corresponding ethyl methyl-diacetoxy-benzoates successively with a 5% sodium bicarbonate solution may also be produced by following the procedures deand twice with $0 ml of water. The solvent is removed scribed in Examples I, II and 111 by using the corresponding ethyl ester of methyl-dihydroxy-benzoic acid. To produce the corresponding ethyl ester, sodium ethylate ethanol solution is employed instead of. sodium methylate methanol solution. In Example 1, sodium ethylate ethanol solution may be prepared by gradually adding 437 g of sodium to about 9,200 ml of ethanol over a period of about 2 hours.

EXAMPLE V Perfume Compositions The following specific examples show the usefulness of the alkyl monomethyl-ringsubstituted-diacetoxybenzoates of Formula I in perfumery:

Chypre Type Perfume Base Parts by Weight 50 Methyl(or ethyl) monomethyl-ringsubstituteddiacetoxy-benzoate 25 Musk Ambrette l Musk Ketone 600 Linalyl Acetate ll0 Phenylethyl Alcohol 75 Coumarin Vanillin 10 Oil Orange Fougere Type Perfume Base 180 Oil Lvaenger 60 Linalyl Acetate 40 Oil Patchouly 70 Oil Vetivert Java 150 Coumarin 75 Amy] Cinnamic Aldehyde 40 Oil Neroli 33 Sclareol 6O Methyl (or ethyl) monomethyl-ringsubstituteddiacetoxy-benzoate Phanthasy Type Perfume Base Parts by Weight 25 Methyl (or ethyl) monomethyl-ringsubstituteddiacetoxy-benzoate 300 Oil Geranium 200 Oil Ylang Ylang 100 Heliotropin 100 Vanillin 25 lso-Eugenol 50 a Amyl-Cinnamic Aldehyde 50 Oil Patchouly 3O Phenylethyl Alcohol 20 Orange Flowers Absolute New Mown Hay Type Perfume Base 20 Methyl(or ethyl)monomethyl-ringsubstituteddiacetoxy-benzoate 50 Dimethyl Hydroquinone 200 Oil Lavender 250 Linalyl Acetate 50 Methyl Salicylate 10 Oil Clary Sage 50 Oil Ylang Ylang 30 Tonka Beans Absolute 10 Oil Patchouly 5 Oil Vetivert 50 Linalool l0 Benzyl Acetate 200 Hydroxycitronellal 5 Diphenyl Oxide 30 Coumarin l0 Vanillin 20 Musk Ketone What is claimed is: 1. A perfume composition comprising at least 1% by weight of an alkyl monomethyl-ringsubstituteddiacetoxy-benzoate and at least 1% by weight of an odoriferous perfume component, said alkyl monomethyl-ringsubstituted-diacetoxy-benzoate having the formula:

COOR

H3CC-O O-C-CH3 in which R is methyl or ethyl.

2. A perfume composition of claim 1 in which the alkyl monomethyl-ringsubstituted-diacetoxy-benzoate comprises 1 to 30% by weight of the perfume composition.

3. A perfume composition of claim 1 in which the alkyl monomethyl-ringsubstituted-diacetoxy-benzoate comprises 2 to 5% by weight of the perfume composition.

4. A perfume composition of claim 1 in which the alkyl monomethyl-ringsubstituted-diacetoxy-benzoate is methyl(or ethyl) 3-methyl-2,4diacetoxy-benzoate.

5. A perfume composition of claim 1 in which the alkyl monomethyl-ringsubstituted-diacetoxy-benzoate is methyl(or ethyl) 6-methyl-2,4-diacetoxy-benzoate.

6. A perfume composition of claim 1 in which the alkyl monomethyl-ringsubstituted-diacetoxy benzoate is methyl(or ethyl) 4-methyl-2,6-diacetoxy-benzoate.

7. A perfume composition of claim 1 in which the alkyl monomethyl-ringsubstituted-diacetoxy-benzoate is methyl(or ethyl) 5-methyl-2,6-diacetoxy-benzoate.

8. A perfume compositionvof claim 1 in which the alkyl monomethyl-ringsubstituted-diacetoxy-benzoate is methyl(or ethyl) 2-methyl-3,S-diacetoxy-benzoate.

9. A perfume composition of claim 1 in which the alkyl monomethyl-ringsubstituted-diacetoxy-benzoate is methyl(or ethyl) 4-m ethyl-3,S-diacetoxy-benzoate.

10. A perfume composition of claim 1 in which the alkyl monomethyl-ringsubstituted-diacetoxy-benzoate is methyl(or ethyl) 3-methyl-4,6-diacetoxy-benzoate. 

1. A PERFUME COMPOSITION COMPRISING AT LEAST 1% BY WEIGHT OF AN ALKYL MONOMETHYL-RINGSUBSTITUTED-DIACETOXY-BENZOATE AND AT LEAST 1% BY WEIGHT OF AN ODORIFEROUS PERFUME COMPONENT, SAID ALKYL MONOMETHYL-RINGSUBSTITUTED-DIACETOXYBENZOATE HAVING THE FORMULA:
 2. A perfume composition of claim 1 in which the alkyl monomethyl-ringsubstituted-diacetoxy-benzoate comprises 1 to 30% by weight of the perfume composition.
 3. A perfume composition of claim 1 in which the alkyl monomethyl-ringsubstituted-diacetoxy-benzoate comprises 2 to 5% by weight of the perfume composition.
 4. A perfume composition of claim 1 in which the alkyl monomethyl-ringsubstituted-diacetoxy-benzoate is methyl(or ethyl) 3-methyl-2,4-diacetoxy-benzoate.
 5. A perfume composition of claim 1 in which the alkyl monomethyl-ringsubstituted-diacetoxy-benzoate is methyl(or ethyl) 6-methyl-2,4-diacetoxy-benzoate.
 6. A perfume composition of claim 1 in which the alkyl monomethyl-ringsubstituted-diacetoxy benzoate is methyl(or ethyl) 4-methyl-2,6-diacetoxy-benzoate.
 7. A perfume composition of claim 1 in which the alkyl monomethyl-ringsubstituted-diacetoxy-benzoate is methyl(or ethyl) 5-methyl-2,6-diacetoxy-benzoate.
 8. A perfume composition of claim 1 in which the alkyl monomethyl-ringsubstituted-diacetoxy-benzoate is methyl(or ethyl) 2-methyl-3,5-diacetoxy-benzoate.
 9. A perfume composition of claim 1 in which the alkyl monomethyl-ringsubstituted-diacetoxy-benzoate is methyl(or ethyl) 4-methyl-3,5-diacetoxy-benzoate.
 10. A perfume composition of claim 1 in which the alkyl monomethyl-ringsubstituted-diacetoxy-benzoate is methyl(or ethyl) 3-methyl-4,6-diacetoxy-benzoate. 